research communications
Crystal structures of two new carbazole derivatives: ethyl 9-(benzenesulfonyl)-2-(4-fluoro-2-nitrophenyl)-6-methoxy-9H-carbazole-3-carboxylate and 12-(benzenesulfonyl)-12H-quinolino[4,3-b]carbazole
aDepartment of Physics, The New College, Chennai 600 014, University of Madras, Tamil Nadu, India, and bDepartment of Organic Chemistry, University of Madras, Guindy Campus, Chennai-600 025, Tamilnadu, India
*Correspondence e-mail: mnizam.new@gmail.com
The title compounds, C28H21FN2O7S (I) and C25H16N2O2S (II), are carbazole derivatives with a benzenesulfonyl group attached to the carbazole moiety at the N atom on both molecules. A fluoro-substituted nitrophenyl ring system in I and a fused isoquinoline ring in II are attached to the respective carbazole moieties. In both compounds, the carbazole ring systems are essentially planar, with maximum deviations of 0.028 (2) and 0.026 (2) Å for carbon atoms in compounds I and II, respectively. The carbazole ring system is almost orthogonal to the benzene ring attached to sulfonyl group, with dihedral angles of 79.7 (2) in I and 88.2 (2)° in II, respectively. The mean planes of the carbazole ring systems make dihedral angles of 66.1 (2) and 1.3 (2)°, respectively, with the nitrophenyl ring in I and the planar isoquinoline moiety [maximum deviation of 0.009 (3) Å for a carbon atom in II, indicating that the ring system in II is essentially planar]. The benzenesulfonyl ring is almost normal to the isoquinoline ring, with a dihedral angle of 87.9 (2)° in II and the nitrophenyl ring forms a dihedral angle of 17.8 (2)° in I. In both compounds, intramolecular C—H⋯O hydrogen bonds generate S(6) ring motifs with the sulfone group O atoms. In crystals of compound I, the molecules are linked by C—H⋯O intermolecular weak hydrogen bonds, which generate C(7) and C(10) chains running parallel to [010] and [100], respectively.
1. Chemical context
Carbazole and its derivatives have been attractive to researchers because of their broad spectrum of biological activities. Beneficial properties include anti-oxidative (Tachibana et al., 2001), antitumor activity against leukaemia, renal tumour, colon cancer and malignant melanoma tumour cell lines (Pindur & Lemster, 1997; Itoigawa et al., 2000), anti-inflammatory and antimutagenic (Ramsewak et al., 1999), antibiotic, antifungal and cytotoxic (Chakraborty et al., 1965; 1978), pim kinase inhibitory (Giraud et al., 2014), antimicrobial (Gu et al., 2014), antimitotic and antioxidative activities (Tachibana et al., 2003; Hu et al., 2006), and anti-Alzheimer's effects (Thiratmatrakul et al., 2014). Carbazole derivatives also exhibit electroactivity and luminescence, and are considered to be potential contenders for electronic applications such as luminescent and hole-transporting materials (Dijken et al., 2004), colour displays (Santhanam & Sundaresan, 1986), organic semiconductors, high-performance blue phosphorescent organic light-emitting diodes (Ye et al., 2010), laser and solar cells (Friend, et al. 1999; Zhang et al. 2004). Carbazole-based heterocyclic polymer systems can be chemically or electrochemically polymerized to give products with a number of applications, such as rechargeable batteries (Sacak, 1999) and molecular glasses, which are widely studied as components of electroactive and photoactive materials (Zhang et al., 2004). Against this background, the X-ray structure determinations of the title compounds, I and II, have been carried out and the results are presented here.
2. Structural commentary
In the molecular structures of the title compounds, C28H21FN2O7S (I), which comprises a carbazole ring system attached to a benzenesulfonyl ring, a fluorine substituted nitrophenyl ring, a methoxy group and an ethylformate group and C25H16N2O2S (II), which comprises a carbazole ring system attached to a benzenesulfonyl ring and fused isoqinoline ring, are illustrated in Figs. 1 and 2, respectively. In both compounds, the carbazole ring systems (N1/C1–C12) are essentially planar, with maximum deviations of 0.028 (2) and 0.026 (2) Å for atom C12 and C4 in compounds I and II, respectively. The carbazole ring system is almost orthogonal to the benzene ring (C20–C25) attached to the sulfonyl group, with dihedral angles of 79.7 (2) in I and 88.2 (2)° in II, respectively. The mean planes of the carbazole ring systems make dihedral angles of 66.1 (2) and 1.3 (2)°, respectively, with the nitrophenyl ring (C13–C18) in I and the planar isoquinoline (N2/C9/C10/C13–C19) moiety [maximum deviation of 0.009 (3) Å for atom C9] in II, indicating that the ring system in II is essentially planar. The benzenesulfonyl ring (C20–C25) is almost normal to the isoquinoline ring (N2/C9/C10/C13–C19), with a dihedral angle of 87.9 (2)° in II. In I, the corresponding dihedral angle with the nitrophenyl ring (C13–C18) is 17.8 (2)°.
In both compounds, the tetrahedral configuration is distorted around sulfur atom S1. The increase in the O2—S1—O1 angle [119.9 (2)° in I and 120.3 (2)° in II], with a simultaneous decrease in the N1—S1—C20 angle [104.7 (2)° in I and 104.9 (2)° in II] from the ideal tetrahedral value (109.5°) are attributed to the Thorpe-Ingold effect (Bassindale, 1984). The widening of the angles may be due to the repulsive interaction between the two short S=O bonds. The N1—C1 distances [1.434 (3) Å in I and 1.435 (3) Å in II] and N1—C12 bond lengths [1.421 (3) Å in I and 1.426 (3) Å in II] in the molecules are longer than the mean Nsp2—Csp2 bond-length value of 1.355 (14) Å (Allen et al., 1987). The elongation observed may be due to the electron-withdrawing character of the benzenesulfonyl group. The sum of the bond angles around N1 (351.7° in I and 356.2° in II) indicate sp2 The geometric parameters of both compounds agree well with those of related structures (Narayanan et al., 2014a,b).
In compound I, the nitro group is (+) syn-periplanar to the benzene ring (atoms C13–C18), as indicated by the values of the torsion angles C13—C14—N2—O6 = −24.6 (4)° and C15—C14—N2—O7 = −24.1 (4)°. The nitrogen atom N2 is almost in the plane of the benzene ring, with a torsion angle C18—C13—C14—N2 of −177.8 (2)°. The fluorine atom forms a torsion angle C14—C15—C16—F1 of 177.9 (2)°, indicating that the fluorine substituent at C16 is almost coplanar with benzene ring C13–C18. The fluorine atom F1 deviates by −0.063 (2) Å from the benzene ring (C13–C18). In both compounds, the molecular structures are stabilized by C2—H2⋯O2 and C11—H11⋯O1 intramolecular interactions involving the sulfone oxygen atoms, which generate two S(6) ring motifs (Fig. 1 and 2).
3. Supramolecular features
In the crystal packing of compound I, molecules are linked by C3—H3⋯O4i and C17—H17⋯O7ii (symmetry codes as per Table 1) intermolecular hydrogen bonds, generating C(7) and C(10) chains running parallel to [010] and [100], respectively. Very weak interactions between inversion-related C13–C18 and C20–C25 rings lead to an inter-centroid distance Cg1⋯Cg2iii of 3.889 (2) Å [Cg1 and Cg2 are the centroids of rings C13–C18 and C20–C25, respectively, symmetry code: (iii) 1 − x, 1 − y, −z]. No significant C—H⋯π interactions with centroid distances of less than ∼4 Å are observed in the structure.
In compound II, the crystal packing is stabilized by C4—H4⋯Cg1ii and C16—H16⋯Cg3iii intermolecular interactions (symmetry codes as per Table 2), where Cg1 and Cg3 are the centres of gravity of rings (C13–C18) and (C7–C12), respectively. Packing plots of I and II are shown in Figs. 3 and 4. The whole of the fused ring system in II π-stacks with that of an inversion-related adjacent molecule, giving an interplanar spacing of 3.492 (3) Å.
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4. Hirshfeld surface analysis
A recent article by Tiekink and collaborators (Tan et al., 2019) reviews and describes the uses and utility of Hirshfeld-surface analysis (Spackman & Jayatilaka, 2009), and the associated two-dimensional fingerprint plots (McKinnon et al., 2007), to analyse intermolecular contacts in crystals. The various analyses (dnorm, curvedness, shape index, and 2D-fingerprint plots) for I and II were performed with CrystalExplorer17 (Turner et al., 2017).
The Hirshfeld surfaces of compounds I and II mapped over dnorm are given in Fig. 5, and the intermolecular contacts are illustrated in Fig. 6a for I and Fig. 7a for II. They are colour-mapped with the normalized contact distance, dnorm, from red (distances shorter than the sum of the van der Waals radii) through white to blue (distances longer than the sum of the van der Waals radii), such that the red spots indicate intermolecular contacts involved in hydrogen bonding. The presence of interactions are indicated by red and blue areas on the shape-index surface (Fig. 6b for I and 7b for II). Areas on the Hirshfeld surface with high curvedness tend to divide the surface into contact patches with the neighbouring molecules. The in the crystal is thus indicated by the curvedness of the Hirshfeld surface (Fig. 6c for I and Fig. 7c for II). The nearest neighbour coordination environment of a molecule is indicated by colour patches on the Hirshfeld surface depending on their closeness to adjacent molecules (Fig. 6d for I and Fig. 7d for II).
Atom-contact fingerprint plots are given in Figs. 8 and 9. For compound I, they reveal the fraction of intermolecular contacts to be H⋯H = 31.0%, O⋯H/H⋯O = 31.0%, C⋯H/H⋯C = 18.9%, F⋯H/H⋯F = 6.3%, C⋯C = 4.9%, C⋯O/O⋯C = 3.4%, N⋯H/H⋯N = 2.3%, and C⋯F/F⋯C = 0.6%). For compound II, they reveal a similar trend, with the fraction of intermolecular contacts being C⋯H/H⋯C = 35.2%, H⋯H = 35.1%, O⋯H/H⋯O = 14.2%, C⋯C = 7.9%, N⋯H/H⋯N contacts = 4.2%, C⋯N/N⋯C contacts = 1.0%, C⋯O/O⋯C = 0.2% and S⋯H/H⋯S = 0.1%.
5. Synthesis and crystallization
Compound I: To a solution of ethyl (E)-3-{2-[(E)-4-fluoro-2-nitrostyryl]-5-methoxy-1-(benzenesulfonyl)-1H-indol-3-yl}acrylate (3.0 g) in xylenes (100 mL), MnO2 (2.5 g) was added, and the reaction mixture was refluxed for 12 h. It was then filtered through a celite pad and washed with hot xylenes (2 × 10 mL). The combined filtrate was concentrated under vacuum and then triturated with MeOH to give compound I (2.46 g, 85%) as a pale-yellow solid, mp: 473–475% K. Crystals of I were obtained by re-crystallization from ethanol.
Compound II: To a solution of 2-(2-nitrophenyl)-9-(benzenesulfonyl)-9H-carbazole-3-carbaldehyde (1.0 g) in dry THF (50 mL), Raney-Ni (2.0 g) was carefully added, and the reaction mixture was stirred at room temperature for 3 h. Then, the nickel residue was carefully filtered through a celite pad and washed with hot THF (3 × 30 mL). The combined filtrate was evaporated under vacuum and then triturated with MeOH to give compound II (0.79 g, 80%) as a white solid, mp: 487–489 K. Crystals suitable for X-ray analysis were obtained by re-crystallization from ethanol.
6. Refinement
Crystal data, data collection and structure . The positions of hydrogen atoms were found in difference electron-density maps. Hydrogen atoms bound to carbon were treated as riding atoms, with d(C—H) = 0.93–0.97 Å and Uiso(H) = 1.2Ueq(C) or Uiso(H) = 1.5Ueq(C) (methyl). Methyl group torsion angles were optimized.
details are summarized in Table 3
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Supporting information
https://doi.org/10.1107/S2056989022010684/pk2671sup1.cif
contains datablocks global, I, II. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989022010684/pk2671Isup4.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2056989022010684/pk2671Isup4.cml
Structure factors: contains datablock II. DOI: https://doi.org/10.1107/S2056989022010684/pk2671IIsup5.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2056989022010684/pk2671IIsup5.cml
For both structures, data collection: APEX3 (Bruker, 2016); cell
APEX3/SAINT (Bruker, 2016); data reduction: SAINT/XPREP (Bruker, 2016); program(s) used to solve structure: SHELXT2018/2 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2020); software used to prepare material for publication: WinGX (Farrugia, 2012), publCIF (Westrip, 2010) and PLATON (Spek, 2020).C28H21FN2O7S | Z = 2 |
Mr = 548.53 | F(000) = 568 |
Triclinic, P1 | Dx = 1.450 Mg m−3 |
a = 8.1589 (9) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 12.2053 (13) Å | Cell parameters from 9133 reflections |
c = 12.9129 (13) Å | θ = 2.9–20.6° |
α = 101.569 (4)° | µ = 0.19 mm−1 |
β = 93.086 (4)° | T = 298 K |
γ = 92.481 (4)° | Solid, pale yellow |
V = 1256.0 (2) Å3 | 0.31 × 0.24 × 0.13 mm |
Bruker D8 Venture diffractometer with Photon II detector | 5194 independent reflections |
Radiation source: fine-focus sealed tube | 4176 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.051 |
ω and φ scan | θmax = 26.5°, θmin = 3.2° |
Absorption correction: multi-scan (SADABS; Bruker, 2016) | h = −10→10 |
Tmin = 0.923, Tmax = 0.965 | k = −15→15 |
31739 measured reflections | l = −16→16 |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.054 | H-atom parameters constrained |
wR(F2) = 0.150 | w = 1/[σ2(Fo2) + (0.0502P)2 + 0.9577P] where P = (Fo2 + 2Fc2)/3 |
S = 1.13 | (Δ/σ)max < 0.001 |
5194 reflections | Δρmax = 0.28 e Å−3 |
354 parameters | Δρmin = −0.38 e Å−3 |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.5947 (3) | 0.82807 (19) | 0.33841 (19) | 0.0432 (5) | |
C2 | 0.5905 (4) | 0.9424 (2) | 0.3415 (2) | 0.0547 (7) | |
H2 | 0.534951 | 0.969581 | 0.287941 | 0.066* | |
C3 | 0.6708 (4) | 1.0137 (2) | 0.4262 (2) | 0.0602 (8) | |
H3 | 0.670280 | 1.090490 | 0.429413 | 0.072* | |
C4 | 0.7534 (4) | 0.9746 (2) | 0.5077 (2) | 0.0550 (7) | |
C5 | 0.7536 (3) | 0.8609 (2) | 0.5069 (2) | 0.0484 (6) | |
H5 | 0.805234 | 0.834352 | 0.562212 | 0.058* | |
C6 | 0.6741 (3) | 0.78757 (18) | 0.42037 (19) | 0.0413 (5) | |
C7 | 0.6522 (3) | 0.66650 (18) | 0.39461 (18) | 0.0384 (5) | |
C8 | 0.7000 (3) | 0.58302 (18) | 0.44653 (18) | 0.0382 (5) | |
H8 | 0.760023 | 0.601797 | 0.511504 | 0.046* | |
C9 | 0.6584 (3) | 0.47101 (18) | 0.40159 (18) | 0.0369 (5) | |
C10 | 0.5673 (3) | 0.44179 (18) | 0.30303 (18) | 0.0369 (5) | |
C11 | 0.5192 (3) | 0.52566 (19) | 0.25104 (19) | 0.0411 (5) | |
H11 | 0.458835 | 0.507465 | 0.186175 | 0.049* | |
C12 | 0.5621 (3) | 0.63664 (18) | 0.29683 (19) | 0.0390 (5) | |
C13 | 0.4990 (3) | 0.32669 (18) | 0.25064 (17) | 0.0359 (5) | |
C14 | 0.5846 (3) | 0.23731 (19) | 0.19937 (19) | 0.0397 (5) | |
C15 | 0.5085 (3) | 0.1383 (2) | 0.1430 (2) | 0.0461 (6) | |
H15 | 0.569368 | 0.080494 | 0.109286 | 0.055* | |
C16 | 0.3402 (3) | 0.1284 (2) | 0.1385 (2) | 0.0479 (6) | |
C17 | 0.2487 (3) | 0.2110 (2) | 0.1896 (2) | 0.0508 (6) | |
H17 | 0.134812 | 0.201332 | 0.187587 | 0.061* | |
C18 | 0.3288 (3) | 0.3093 (2) | 0.2444 (2) | 0.0441 (5) | |
H18 | 0.266421 | 0.366080 | 0.278478 | 0.053* | |
C19 | 0.7117 (3) | 0.38165 (19) | 0.45764 (19) | 0.0422 (5) | |
C20 | 0.6890 (3) | 0.7300 (2) | 0.0857 (2) | 0.0506 (6) | |
C21 | 0.7943 (4) | 0.8241 (3) | 0.1038 (2) | 0.0722 (9) | |
H21 | 0.761507 | 0.893146 | 0.138596 | 0.087* | |
C22 | 0.9537 (6) | 0.8117 (5) | 0.0674 (3) | 0.1089 (18) | |
H22 | 1.029701 | 0.872575 | 0.079031 | 0.131* | |
C23 | 0.9955 (6) | 0.7078 (7) | 0.0144 (3) | 0.120 (2) | |
H23 | 1.101471 | 0.699221 | −0.008005 | 0.143* | |
C24 | 0.8868 (7) | 0.6181 (5) | −0.0060 (3) | 0.1110 (17) | |
H24 | 0.916615 | 0.550314 | −0.045527 | 0.133* | |
C25 | 0.7336 (5) | 0.6269 (3) | 0.0313 (3) | 0.0739 (9) | |
H25 | 0.660166 | 0.564583 | 0.020359 | 0.089* | |
C26 | 0.9088 (6) | 1.0250 (3) | 0.6723 (3) | 0.0956 (14) | |
H26A | 0.830154 | 0.991505 | 0.711004 | 0.143* | |
H26B | 0.962806 | 1.089934 | 0.717734 | 0.143* | |
H26C | 0.988796 | 0.971938 | 0.647947 | 0.143* | |
C27 | 0.8536 (4) | 0.3375 (2) | 0.6062 (2) | 0.0535 (7) | |
H27A | 0.934315 | 0.294924 | 0.565185 | 0.064* | |
H27B | 0.764671 | 0.286048 | 0.616283 | 0.064* | |
C28 | 0.9307 (4) | 0.3968 (3) | 0.7108 (2) | 0.0673 (8) | |
H28A | 1.013542 | 0.451088 | 0.700178 | 0.101* | |
H28B | 0.980023 | 0.343642 | 0.746679 | 0.101* | |
H28C | 0.848189 | 0.434050 | 0.752872 | 0.101* | |
N1 | 0.5207 (3) | 0.73549 (16) | 0.26146 (17) | 0.0445 (5) | |
N2 | 0.7653 (3) | 0.2432 (2) | 0.2032 (2) | 0.0580 (6) | |
O1 | 0.3949 (3) | 0.64184 (17) | 0.08549 (17) | 0.0671 (6) | |
O2 | 0.4347 (3) | 0.84684 (17) | 0.12977 (17) | 0.0676 (6) | |
O3 | 0.8282 (3) | 1.05644 (16) | 0.58552 (18) | 0.0792 (7) | |
O4 | 0.6862 (3) | 0.28366 (15) | 0.42290 (17) | 0.0798 (8) | |
O5 | 0.7909 (2) | 0.42120 (13) | 0.55099 (14) | 0.0494 (4) | |
O6 | 0.8380 (3) | 0.33442 (19) | 0.2187 (2) | 0.0800 (7) | |
O7 | 0.8334 (3) | 0.1550 (2) | 0.1902 (3) | 0.0957 (9) | |
S1 | 0.49241 (8) | 0.73975 (5) | 0.13348 (5) | 0.0483 (2) | |
F1 | 0.2637 (2) | 0.03387 (13) | 0.08098 (16) | 0.0748 (6) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0559 (15) | 0.0285 (11) | 0.0468 (13) | 0.0031 (10) | 0.0074 (11) | 0.0106 (10) |
C2 | 0.0776 (19) | 0.0340 (13) | 0.0562 (16) | 0.0105 (12) | 0.0076 (14) | 0.0156 (11) |
C3 | 0.093 (2) | 0.0257 (12) | 0.0631 (17) | 0.0059 (13) | 0.0135 (16) | 0.0100 (11) |
C4 | 0.079 (2) | 0.0314 (13) | 0.0523 (15) | −0.0046 (12) | 0.0100 (14) | 0.0029 (11) |
C5 | 0.0657 (17) | 0.0318 (12) | 0.0465 (14) | −0.0009 (11) | 0.0030 (12) | 0.0058 (10) |
C6 | 0.0529 (14) | 0.0288 (11) | 0.0435 (13) | 0.0018 (10) | 0.0076 (10) | 0.0096 (9) |
C7 | 0.0481 (13) | 0.0276 (11) | 0.0405 (12) | 0.0004 (9) | 0.0048 (10) | 0.0092 (9) |
C8 | 0.0482 (13) | 0.0292 (11) | 0.0376 (11) | 0.0007 (9) | 0.0017 (10) | 0.0086 (9) |
C9 | 0.0443 (12) | 0.0296 (11) | 0.0385 (12) | 0.0012 (9) | 0.0044 (9) | 0.0104 (9) |
C10 | 0.0420 (12) | 0.0292 (11) | 0.0401 (12) | −0.0001 (9) | 0.0052 (9) | 0.0081 (9) |
C11 | 0.0480 (13) | 0.0348 (12) | 0.0404 (12) | −0.0019 (10) | −0.0029 (10) | 0.0099 (9) |
C12 | 0.0456 (13) | 0.0305 (11) | 0.0439 (12) | 0.0007 (9) | 0.0023 (10) | 0.0154 (9) |
C13 | 0.0411 (12) | 0.0292 (11) | 0.0385 (11) | −0.0011 (9) | 0.0011 (9) | 0.0107 (9) |
C14 | 0.0394 (12) | 0.0350 (12) | 0.0443 (12) | −0.0005 (9) | 0.0022 (10) | 0.0078 (9) |
C15 | 0.0554 (15) | 0.0312 (12) | 0.0497 (14) | 0.0025 (10) | −0.0027 (11) | 0.0048 (10) |
C16 | 0.0517 (15) | 0.0316 (12) | 0.0585 (15) | −0.0067 (10) | −0.0146 (12) | 0.0110 (11) |
C17 | 0.0379 (13) | 0.0437 (14) | 0.0729 (18) | −0.0046 (11) | −0.0077 (12) | 0.0214 (13) |
C18 | 0.0414 (13) | 0.0374 (12) | 0.0554 (14) | 0.0046 (10) | 0.0038 (11) | 0.0135 (11) |
C19 | 0.0546 (14) | 0.0307 (12) | 0.0427 (13) | 0.0006 (10) | 0.0019 (11) | 0.0113 (9) |
C20 | 0.0607 (16) | 0.0537 (15) | 0.0379 (13) | 0.0025 (12) | −0.0091 (11) | 0.0141 (11) |
C21 | 0.074 (2) | 0.091 (2) | 0.0472 (16) | −0.0215 (18) | −0.0042 (15) | 0.0091 (16) |
C22 | 0.081 (3) | 0.191 (5) | 0.052 (2) | −0.043 (3) | −0.0110 (19) | 0.033 (3) |
C23 | 0.078 (3) | 0.235 (7) | 0.050 (2) | 0.042 (4) | −0.001 (2) | 0.035 (3) |
C24 | 0.122 (4) | 0.153 (5) | 0.064 (2) | 0.075 (4) | 0.005 (3) | 0.023 (3) |
C25 | 0.098 (3) | 0.071 (2) | 0.0551 (18) | 0.0295 (19) | −0.0012 (17) | 0.0137 (15) |
C26 | 0.144 (4) | 0.065 (2) | 0.068 (2) | −0.032 (2) | −0.022 (2) | 0.0060 (18) |
C27 | 0.0665 (17) | 0.0436 (14) | 0.0554 (16) | 0.0101 (12) | −0.0020 (13) | 0.0220 (12) |
C28 | 0.076 (2) | 0.072 (2) | 0.0559 (17) | 0.0126 (16) | −0.0095 (15) | 0.0197 (15) |
N1 | 0.0546 (12) | 0.0305 (10) | 0.0508 (12) | 0.0017 (9) | −0.0021 (9) | 0.0155 (9) |
N2 | 0.0448 (13) | 0.0518 (14) | 0.0717 (16) | −0.0017 (11) | 0.0119 (11) | −0.0023 (11) |
O1 | 0.0753 (14) | 0.0557 (12) | 0.0692 (13) | −0.0174 (10) | −0.0300 (11) | 0.0238 (10) |
O2 | 0.0830 (15) | 0.0528 (12) | 0.0743 (14) | 0.0187 (10) | −0.0081 (11) | 0.0302 (10) |
O3 | 0.128 (2) | 0.0355 (10) | 0.0670 (14) | −0.0149 (11) | −0.0070 (13) | 0.0004 (9) |
O4 | 0.142 (2) | 0.0282 (10) | 0.0659 (13) | −0.0011 (11) | −0.0335 (13) | 0.0130 (9) |
O5 | 0.0695 (12) | 0.0319 (8) | 0.0475 (10) | 0.0026 (8) | −0.0100 (8) | 0.0134 (7) |
O6 | 0.0534 (12) | 0.0631 (14) | 0.1118 (19) | −0.0173 (11) | 0.0258 (12) | −0.0109 (13) |
O7 | 0.0493 (13) | 0.0665 (15) | 0.163 (3) | 0.0153 (11) | 0.0119 (15) | −0.0009 (16) |
S1 | 0.0555 (4) | 0.0389 (3) | 0.0527 (4) | 0.0009 (3) | −0.0122 (3) | 0.0189 (3) |
F1 | 0.0759 (12) | 0.0370 (8) | 0.1018 (14) | −0.0127 (8) | −0.0333 (10) | 0.0047 (8) |
C1—C2 | 1.390 (3) | C17—H17 | 0.9300 |
C1—C6 | 1.396 (3) | C18—H18 | 0.9300 |
C1—N1 | 1.434 (3) | C19—O4 | 1.195 (3) |
C2—C3 | 1.369 (4) | C19—O5 | 1.326 (3) |
C2—H2 | 0.9300 | C20—C21 | 1.377 (4) |
C3—C4 | 1.395 (4) | C20—C25 | 1.387 (4) |
C3—H3 | 0.9300 | C20—S1 | 1.749 (3) |
C4—O3 | 1.363 (3) | C21—C22 | 1.411 (6) |
C4—C5 | 1.386 (3) | C21—H21 | 0.9300 |
C5—C6 | 1.393 (3) | C22—C23 | 1.381 (8) |
C5—H5 | 0.9300 | C22—H22 | 0.9300 |
C6—C7 | 1.449 (3) | C23—C24 | 1.352 (7) |
C7—C8 | 1.386 (3) | C23—H23 | 0.9300 |
C7—C12 | 1.400 (3) | C24—C25 | 1.365 (6) |
C8—C9 | 1.393 (3) | C24—H24 | 0.9300 |
C8—H8 | 0.9300 | C25—H25 | 0.9300 |
C9—C10 | 1.412 (3) | C26—O3 | 1.397 (4) |
C9—C19 | 1.492 (3) | C26—H26A | 0.9600 |
C10—C11 | 1.391 (3) | C26—H26B | 0.9600 |
C10—C13 | 1.501 (3) | C26—H26C | 0.9600 |
C11—C12 | 1.387 (3) | C27—O5 | 1.454 (3) |
C11—H11 | 0.9300 | C27—C28 | 1.490 (4) |
C12—N1 | 1.421 (3) | C27—H27A | 0.9700 |
C13—C18 | 1.392 (3) | C27—H27B | 0.9700 |
C13—C14 | 1.393 (3) | C28—H28A | 0.9600 |
C14—C15 | 1.381 (3) | C28—H28B | 0.9600 |
C14—N2 | 1.471 (3) | C28—H28C | 0.9600 |
C15—C16 | 1.371 (4) | N1—S1 | 1.668 (2) |
C15—H15 | 0.9300 | N2—O6 | 1.213 (3) |
C16—F1 | 1.348 (3) | N2—O7 | 1.219 (3) |
C16—C17 | 1.363 (4) | O1—S1 | 1.419 (2) |
C17—C18 | 1.382 (3) | O2—S1 | 1.4172 (19) |
C2—C1—C6 | 121.1 (2) | O4—C19—O5 | 122.6 (2) |
C2—C1—N1 | 129.8 (2) | O4—C19—C9 | 124.0 (2) |
C6—C1—N1 | 109.12 (19) | O5—C19—C9 | 113.48 (19) |
C3—C2—C1 | 117.7 (3) | C21—C20—C25 | 122.3 (3) |
C3—C2—H2 | 121.1 | C21—C20—S1 | 119.3 (2) |
C1—C2—H2 | 121.1 | C25—C20—S1 | 118.5 (3) |
C2—C3—C4 | 121.9 (2) | C20—C21—C22 | 117.5 (4) |
C2—C3—H3 | 119.0 | C20—C21—H21 | 121.3 |
C4—C3—H3 | 119.0 | C22—C21—H21 | 121.3 |
O3—C4—C5 | 124.8 (3) | C23—C22—C21 | 119.1 (4) |
O3—C4—C3 | 114.5 (2) | C23—C22—H22 | 120.5 |
C5—C4—C3 | 120.7 (3) | C21—C22—H22 | 120.5 |
C4—C5—C6 | 117.8 (2) | C24—C23—C22 | 122.0 (5) |
C4—C5—H5 | 121.1 | C24—C23—H23 | 119.0 |
C6—C5—H5 | 121.1 | C22—C23—H23 | 119.0 |
C5—C6—C1 | 120.8 (2) | C23—C24—C25 | 120.1 (5) |
C5—C6—C7 | 131.9 (2) | C23—C24—H24 | 119.9 |
C1—C6—C7 | 107.3 (2) | C25—C24—H24 | 119.9 |
C8—C7—C12 | 119.1 (2) | C24—C25—C20 | 119.0 (4) |
C8—C7—C6 | 133.2 (2) | C24—C25—H25 | 120.5 |
C12—C7—C6 | 107.7 (2) | C20—C25—H25 | 120.5 |
C7—C8—C9 | 120.1 (2) | O3—C26—H26A | 109.5 |
C7—C8—H8 | 119.9 | O3—C26—H26B | 109.5 |
C9—C8—H8 | 119.9 | H26A—C26—H26B | 109.5 |
C8—C9—C10 | 120.3 (2) | O3—C26—H26C | 109.5 |
C8—C9—C19 | 119.7 (2) | H26A—C26—H26C | 109.5 |
C10—C9—C19 | 120.0 (2) | H26B—C26—H26C | 109.5 |
C11—C10—C9 | 119.5 (2) | O5—C27—C28 | 108.0 (2) |
C11—C10—C13 | 114.0 (2) | O5—C27—H27A | 110.1 |
C9—C10—C13 | 126.16 (19) | C28—C27—H27A | 110.1 |
C12—C11—C10 | 119.4 (2) | O5—C27—H27B | 110.1 |
C12—C11—H11 | 120.3 | C28—C27—H27B | 110.1 |
C10—C11—H11 | 120.3 | H27A—C27—H27B | 108.4 |
C11—C12—C7 | 121.5 (2) | C27—C28—H28A | 109.5 |
C11—C12—N1 | 129.3 (2) | C27—C28—H28B | 109.5 |
C7—C12—N1 | 109.07 (19) | H28A—C28—H28B | 109.5 |
C18—C13—C14 | 115.5 (2) | C27—C28—H28C | 109.5 |
C18—C13—C10 | 116.5 (2) | H28A—C28—H28C | 109.5 |
C14—C13—C10 | 127.7 (2) | H28B—C28—H28C | 109.5 |
C15—C14—C13 | 123.4 (2) | C12—N1—C1 | 106.72 (19) |
C15—C14—N2 | 115.6 (2) | C12—N1—S1 | 122.61 (17) |
C13—C14—N2 | 121.0 (2) | C1—N1—S1 | 122.44 (16) |
C16—C15—C14 | 117.6 (2) | O6—N2—O7 | 123.7 (2) |
C16—C15—H15 | 121.2 | O6—N2—C14 | 118.9 (2) |
C14—C15—H15 | 121.2 | O7—N2—C14 | 117.4 (2) |
F1—C16—C17 | 119.4 (2) | C4—O3—C26 | 118.4 (2) |
F1—C16—C15 | 118.4 (2) | C19—O5—C27 | 115.66 (19) |
C17—C16—C15 | 122.1 (2) | O2—S1—O1 | 119.94 (13) |
C16—C17—C18 | 118.6 (2) | O2—S1—N1 | 106.24 (12) |
C16—C17—H17 | 120.7 | O1—S1—N1 | 106.37 (11) |
C18—C17—H17 | 120.7 | O2—S1—C20 | 109.43 (14) |
C17—C18—C13 | 122.6 (2) | O1—S1—C20 | 109.01 (14) |
C17—C18—H18 | 118.7 | N1—S1—C20 | 104.74 (11) |
C13—C18—H18 | 118.7 | ||
C6—C1—C2—C3 | 1.9 (4) | C15—C16—C17—C18 | 2.4 (4) |
N1—C1—C2—C3 | 178.9 (3) | C16—C17—C18—C13 | −0.9 (4) |
C1—C2—C3—C4 | −0.6 (5) | C14—C13—C18—C17 | −1.1 (3) |
C2—C3—C4—O3 | 179.4 (3) | C10—C13—C18—C17 | 173.7 (2) |
C2—C3—C4—C5 | −1.5 (5) | C8—C9—C19—O4 | −177.3 (3) |
O3—C4—C5—C6 | −178.7 (3) | C10—C9—C19—O4 | 2.2 (4) |
C3—C4—C5—C6 | 2.3 (4) | C8—C9—C19—O5 | 2.9 (3) |
C4—C5—C6—C1 | −1.0 (4) | C10—C9—C19—O5 | −177.6 (2) |
C4—C5—C6—C7 | 179.7 (3) | C25—C20—C21—C22 | −1.9 (4) |
C2—C1—C6—C5 | −1.1 (4) | S1—C20—C21—C22 | 177.6 (2) |
N1—C1—C6—C5 | −178.7 (2) | C20—C21—C22—C23 | 1.2 (5) |
C2—C1—C6—C7 | 178.4 (2) | C21—C22—C23—C24 | 1.6 (6) |
N1—C1—C6—C7 | 0.8 (3) | C22—C23—C24—C25 | −3.8 (7) |
C5—C6—C7—C8 | 0.9 (5) | C23—C24—C25—C20 | 3.1 (6) |
C1—C6—C7—C8 | −178.5 (3) | C21—C20—C25—C24 | −0.2 (5) |
C5—C6—C7—C12 | −179.8 (3) | S1—C20—C25—C24 | −179.7 (3) |
C1—C6—C7—C12 | 0.9 (3) | C11—C12—N1—C1 | 179.3 (2) |
C12—C7—C8—C9 | −0.1 (4) | C7—C12—N1—C1 | 2.6 (3) |
C6—C7—C8—C9 | 179.2 (2) | C11—C12—N1—S1 | −31.7 (4) |
C7—C8—C9—C10 | 0.0 (3) | C7—C12—N1—S1 | 151.62 (18) |
C7—C8—C9—C19 | 179.5 (2) | C2—C1—N1—C12 | −179.4 (3) |
C8—C9—C10—C11 | 0.0 (3) | C6—C1—N1—C12 | −2.1 (3) |
C19—C9—C10—C11 | −179.5 (2) | C2—C1—N1—S1 | 31.5 (4) |
C8—C9—C10—C13 | −173.3 (2) | C6—C1—N1—S1 | −151.14 (19) |
C19—C9—C10—C13 | 7.2 (4) | C15—C14—N2—O6 | 155.8 (3) |
C9—C10—C11—C12 | 0.2 (4) | C13—C14—N2—O6 | −24.6 (4) |
C13—C10—C11—C12 | 174.2 (2) | C15—C14—N2—O7 | −24.1 (4) |
C10—C11—C12—C7 | −0.3 (4) | C13—C14—N2—O7 | 155.5 (3) |
C10—C11—C12—N1 | −176.7 (2) | C5—C4—O3—C26 | −1.4 (5) |
C8—C7—C12—C11 | 0.2 (4) | C3—C4—O3—C26 | 177.7 (3) |
C6—C7—C12—C11 | −179.2 (2) | O4—C19—O5—C27 | 3.4 (4) |
C8—C7—C12—N1 | 177.3 (2) | C9—C19—O5—C27 | −176.7 (2) |
C6—C7—C12—N1 | −2.2 (3) | C28—C27—O5—C19 | −177.3 (2) |
C11—C10—C13—C18 | −62.6 (3) | C12—N1—S1—O2 | 173.3 (2) |
C9—C10—C13—C18 | 110.9 (3) | C1—N1—S1—O2 | −42.4 (2) |
C11—C10—C13—C14 | 111.5 (3) | C12—N1—S1—O1 | 44.5 (2) |
C9—C10—C13—C14 | −75.0 (3) | C1—N1—S1—O1 | −171.3 (2) |
C18—C13—C14—C15 | 1.8 (3) | C12—N1—S1—C20 | −70.9 (2) |
C10—C13—C14—C15 | −172.4 (2) | C1—N1—S1—C20 | 73.4 (2) |
C18—C13—C14—N2 | −177.8 (2) | C21—C20—S1—O2 | 33.8 (3) |
C10—C13—C14—N2 | 8.1 (4) | C25—C20—S1—O2 | −146.8 (2) |
C13—C14—C15—C16 | −0.4 (4) | C21—C20—S1—O1 | 166.7 (2) |
N2—C14—C15—C16 | 179.1 (2) | C25—C20—S1—O1 | −13.8 (2) |
C14—C15—C16—F1 | 177.9 (2) | C21—C20—S1—N1 | −79.8 (2) |
C14—C15—C16—C17 | −1.7 (4) | C25—C20—S1—N1 | 99.7 (2) |
F1—C16—C17—C18 | −177.2 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2···O2 | 0.93 | 2.36 | 2.945 (4) | 121 |
C3—H3···O4i | 0.93 | 2.37 | 3.301 (3) | 174 |
C11—H11···O1 | 0.93 | 2.35 | 2.952 (3) | 123 |
C17—H17···O7ii | 0.93 | 2.50 | 3.428 (3) | 173 |
Symmetry codes: (i) x, y+1, z; (ii) x−1, y, z. |
C25H16N2O2S | F(000) = 848 |
Mr = 408.46 | Dx = 1.410 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 10.142 (1) Å | Cell parameters from 9986 reflections |
b = 12.097 (1) Å | θ = 2.7–29.5° |
c = 16.2218 (15) Å | µ = 0.19 mm−1 |
β = 104.846 (4)° | T = 296 K |
V = 1923.8 (3) Å3 | Solid, colourless |
Z = 4 | 0.40 × 0.35 × 0.25 mm |
Bruker D8 Venture diffractometer with Photon II detector | 4185 independent reflections |
Radiation source: fine-focus sealed tube | 3488 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.051 |
ω and φ scan | θmax = 27.0°, θmin = 3.3° |
Absorption correction: multi-scan (SADABS; Bruker, 2016) | h = −12→12 |
Tmin = 0.867, Tmax = 0.957 | k = −15→15 |
60289 measured reflections | l = −20→20 |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.054 | H-atom parameters constrained |
wR(F2) = 0.161 | w = 1/[σ2(Fo2) + (0.0465P)2 + 2.5552P] where P = (Fo2 + 2Fc2)/3 |
S = 1.13 | (Δ/σ)max < 0.001 |
4185 reflections | Δρmax = 0.32 e Å−3 |
271 parameters | Δρmin = −0.44 e Å−3 |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.8659 (3) | 0.1951 (2) | 0.62473 (17) | 0.0405 (6) | |
C2 | 0.8576 (3) | 0.1281 (3) | 0.69302 (19) | 0.0518 (7) | |
H2 | 0.796204 | 0.142990 | 0.725444 | 0.062* | |
C3 | 0.9447 (3) | 0.0387 (3) | 0.7104 (2) | 0.0592 (8) | |
H3 | 0.941923 | −0.007334 | 0.755800 | 0.071* | |
C4 | 1.0364 (3) | 0.0151 (3) | 0.6623 (2) | 0.0576 (8) | |
H4 | 1.094393 | −0.045445 | 0.676287 | 0.069* | |
C5 | 1.0418 (3) | 0.0807 (2) | 0.5943 (2) | 0.0515 (7) | |
H5 | 1.102062 | 0.064446 | 0.561328 | 0.062* | |
C6 | 0.9560 (3) | 0.1717 (2) | 0.57542 (16) | 0.0391 (5) | |
C7 | 0.9415 (2) | 0.2576 (2) | 0.51200 (16) | 0.0368 (5) | |
C8 | 1.0084 (3) | 0.2769 (2) | 0.44958 (17) | 0.0427 (6) | |
H8 | 1.075496 | 0.228451 | 0.441961 | 0.051* | |
C9 | 0.9744 (3) | 0.3705 (2) | 0.39769 (16) | 0.0392 (6) | |
C10 | 0.8736 (2) | 0.4456 (2) | 0.40903 (15) | 0.0340 (5) | |
C11 | 0.8069 (3) | 0.4262 (2) | 0.47373 (15) | 0.0363 (5) | |
H11 | 0.741028 | 0.474851 | 0.482689 | 0.044* | |
C12 | 0.8418 (2) | 0.3330 (2) | 0.52353 (15) | 0.0340 (5) | |
C13 | 0.8459 (2) | 0.5400 (2) | 0.35213 (15) | 0.0372 (5) | |
C14 | 0.7505 (3) | 0.6228 (2) | 0.35608 (18) | 0.0457 (6) | |
H14 | 0.701230 | 0.617974 | 0.397050 | 0.055* | |
C15 | 0.7285 (3) | 0.7109 (3) | 0.3006 (2) | 0.0543 (7) | |
H15 | 0.664791 | 0.764658 | 0.304288 | 0.065* | |
C16 | 0.8013 (3) | 0.7197 (3) | 0.2390 (2) | 0.0562 (8) | |
H16 | 0.786655 | 0.779570 | 0.201767 | 0.067* | |
C17 | 0.8941 (3) | 0.6405 (3) | 0.2332 (2) | 0.0533 (7) | |
H17 | 0.941880 | 0.646462 | 0.191462 | 0.064* | |
C18 | 0.9187 (3) | 0.5501 (2) | 0.28923 (17) | 0.0432 (6) | |
C19 | 1.0408 (3) | 0.3910 (3) | 0.33103 (19) | 0.0523 (7) | |
H19 | 1.107016 | 0.340809 | 0.324773 | 0.063* | |
C20 | 0.5258 (3) | 0.2476 (3) | 0.54943 (17) | 0.0464 (6) | |
C21 | 0.4892 (3) | 0.1494 (3) | 0.5817 (2) | 0.0557 (8) | |
H21 | 0.529794 | 0.128664 | 0.637693 | 0.067* | |
C22 | 0.3916 (4) | 0.0826 (3) | 0.5298 (3) | 0.0770 (11) | |
H22 | 0.364572 | 0.017708 | 0.551609 | 0.092* | |
C23 | 0.3347 (4) | 0.1110 (5) | 0.4470 (3) | 0.0920 (16) | |
H23 | 0.270298 | 0.064956 | 0.412217 | 0.110* | |
C24 | 0.3727 (4) | 0.2082 (5) | 0.4147 (3) | 0.0880 (15) | |
H24 | 0.333913 | 0.226625 | 0.358053 | 0.106* | |
C25 | 0.4677 (3) | 0.2788 (4) | 0.4653 (2) | 0.0656 (9) | |
H25 | 0.491861 | 0.344837 | 0.443700 | 0.079* | |
N1 | 0.7952 (2) | 0.29582 (18) | 0.59462 (14) | 0.0400 (5) | |
N2 | 1.0159 (3) | 0.4741 (2) | 0.27880 (17) | 0.0562 (7) | |
O1 | 0.6239 (2) | 0.44428 (18) | 0.58737 (15) | 0.0610 (6) | |
O2 | 0.6604 (2) | 0.30363 (18) | 0.70130 (12) | 0.0553 (5) | |
S1 | 0.64894 (7) | 0.33247 (6) | 0.61490 (4) | 0.0440 (2) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0408 (13) | 0.0378 (13) | 0.0409 (13) | 0.0012 (11) | 0.0070 (11) | 0.0004 (10) |
C2 | 0.0532 (17) | 0.0534 (17) | 0.0502 (16) | 0.0005 (14) | 0.0156 (13) | 0.0084 (13) |
C3 | 0.0629 (19) | 0.0517 (18) | 0.0594 (18) | −0.0013 (15) | 0.0089 (15) | 0.0174 (15) |
C4 | 0.0558 (18) | 0.0442 (16) | 0.067 (2) | 0.0085 (14) | 0.0056 (15) | 0.0108 (14) |
C5 | 0.0474 (16) | 0.0465 (16) | 0.0583 (17) | 0.0119 (13) | 0.0097 (13) | 0.0023 (13) |
C6 | 0.0380 (13) | 0.0377 (13) | 0.0392 (13) | 0.0019 (10) | 0.0056 (10) | −0.0006 (10) |
C7 | 0.0323 (12) | 0.0378 (13) | 0.0386 (12) | 0.0026 (10) | 0.0061 (10) | −0.0032 (10) |
C8 | 0.0375 (13) | 0.0437 (14) | 0.0492 (15) | 0.0108 (11) | 0.0156 (11) | −0.0018 (11) |
C9 | 0.0358 (13) | 0.0451 (14) | 0.0386 (13) | 0.0029 (11) | 0.0131 (10) | −0.0029 (11) |
C10 | 0.0328 (11) | 0.0337 (12) | 0.0344 (12) | −0.0022 (9) | 0.0064 (9) | −0.0052 (9) |
C11 | 0.0374 (12) | 0.0339 (12) | 0.0393 (13) | 0.0030 (10) | 0.0129 (10) | −0.0036 (10) |
C12 | 0.0325 (11) | 0.0363 (12) | 0.0336 (11) | 0.0011 (10) | 0.0093 (9) | −0.0038 (9) |
C13 | 0.0360 (12) | 0.0379 (13) | 0.0361 (12) | −0.0052 (10) | 0.0061 (10) | −0.0041 (10) |
C14 | 0.0477 (15) | 0.0428 (14) | 0.0475 (15) | 0.0013 (12) | 0.0138 (12) | 0.0013 (12) |
C15 | 0.0539 (17) | 0.0420 (15) | 0.0649 (19) | 0.0036 (13) | 0.0114 (14) | 0.0058 (14) |
C16 | 0.0565 (18) | 0.0482 (17) | 0.0610 (19) | −0.0062 (14) | 0.0096 (14) | 0.0149 (14) |
C17 | 0.0498 (16) | 0.0584 (18) | 0.0536 (17) | −0.0098 (14) | 0.0169 (13) | 0.0094 (14) |
C18 | 0.0402 (14) | 0.0464 (15) | 0.0437 (14) | −0.0050 (11) | 0.0118 (11) | 0.0009 (11) |
C19 | 0.0480 (16) | 0.0606 (18) | 0.0554 (17) | 0.0123 (14) | 0.0263 (13) | 0.0040 (14) |
C20 | 0.0378 (13) | 0.0620 (18) | 0.0432 (14) | 0.0135 (12) | 0.0174 (11) | −0.0015 (13) |
C21 | 0.0441 (16) | 0.0581 (18) | 0.068 (2) | 0.0082 (14) | 0.0211 (14) | −0.0037 (15) |
C22 | 0.051 (2) | 0.070 (2) | 0.111 (3) | −0.0021 (17) | 0.024 (2) | −0.020 (2) |
C23 | 0.0415 (19) | 0.116 (4) | 0.112 (4) | 0.010 (2) | 0.008 (2) | −0.048 (3) |
C24 | 0.049 (2) | 0.148 (5) | 0.059 (2) | 0.032 (3) | −0.0014 (16) | −0.021 (3) |
C25 | 0.0470 (17) | 0.098 (3) | 0.0527 (18) | 0.0202 (18) | 0.0141 (14) | 0.0052 (18) |
N1 | 0.0420 (12) | 0.0391 (11) | 0.0415 (11) | 0.0061 (9) | 0.0155 (9) | 0.0025 (9) |
N2 | 0.0544 (15) | 0.0668 (17) | 0.0552 (15) | 0.0032 (13) | 0.0283 (12) | 0.0068 (13) |
O1 | 0.0772 (15) | 0.0467 (12) | 0.0726 (14) | 0.0203 (11) | 0.0439 (12) | 0.0080 (10) |
O2 | 0.0696 (14) | 0.0626 (13) | 0.0396 (10) | 0.0056 (11) | 0.0249 (10) | −0.0039 (9) |
S1 | 0.0508 (4) | 0.0455 (4) | 0.0419 (4) | 0.0091 (3) | 0.0230 (3) | 0.0002 (3) |
C1—C6 | 1.389 (4) | C14—H14 | 0.9300 |
C1—C2 | 1.392 (4) | C15—C16 | 1.390 (5) |
C1—N1 | 1.435 (3) | C15—H15 | 0.9300 |
C2—C3 | 1.379 (4) | C16—C17 | 1.364 (5) |
C2—H2 | 0.9300 | C16—H16 | 0.9300 |
C3—C4 | 1.387 (5) | C17—C18 | 1.403 (4) |
C3—H3 | 0.9300 | C17—H17 | 0.9300 |
C4—C5 | 1.372 (4) | C18—N2 | 1.390 (4) |
C4—H4 | 0.9300 | C19—N2 | 1.297 (4) |
C5—C6 | 1.388 (4) | C19—H19 | 0.9300 |
C5—H5 | 0.9300 | C20—C21 | 1.387 (4) |
C6—C7 | 1.444 (4) | C20—C25 | 1.393 (4) |
C7—C8 | 1.376 (4) | C20—S1 | 1.750 (3) |
C7—C12 | 1.409 (3) | C21—C22 | 1.384 (5) |
C8—C9 | 1.400 (4) | C21—H21 | 0.9300 |
C8—H8 | 0.9300 | C22—C23 | 1.364 (6) |
C9—C10 | 1.415 (3) | C22—H22 | 0.9300 |
C9—C19 | 1.435 (4) | C23—C24 | 1.381 (7) |
C10—C11 | 1.407 (3) | C23—H23 | 0.9300 |
C10—C13 | 1.450 (3) | C24—C25 | 1.388 (6) |
C11—C12 | 1.379 (3) | C24—H24 | 0.9300 |
C11—H11 | 0.9300 | C25—H25 | 0.9300 |
C12—N1 | 1.426 (3) | N1—S1 | 1.660 (2) |
C13—C14 | 1.405 (4) | O1—S1 | 1.427 (2) |
C13—C18 | 1.409 (4) | O2—S1 | 1.420 (2) |
C14—C15 | 1.375 (4) | ||
C6—C1—C2 | 121.5 (3) | C14—C15—H15 | 119.9 |
C6—C1—N1 | 108.8 (2) | C16—C15—H15 | 119.9 |
C2—C1—N1 | 129.7 (3) | C17—C16—C15 | 119.9 (3) |
C3—C2—C1 | 116.9 (3) | C17—C16—H16 | 120.0 |
C3—C2—H2 | 121.6 | C15—C16—H16 | 120.0 |
C1—C2—H2 | 121.6 | C16—C17—C18 | 120.9 (3) |
C2—C3—C4 | 122.2 (3) | C16—C17—H17 | 119.5 |
C2—C3—H3 | 118.9 | C18—C17—H17 | 119.5 |
C4—C3—H3 | 118.9 | N2—C18—C17 | 116.7 (3) |
C5—C4—C3 | 120.2 (3) | N2—C18—C13 | 123.4 (2) |
C5—C4—H4 | 119.9 | C17—C18—C13 | 119.9 (3) |
C3—C4—H4 | 119.9 | N2—C19—C9 | 125.2 (3) |
C4—C5—C6 | 118.9 (3) | N2—C19—H19 | 117.4 |
C4—C5—H5 | 120.5 | C9—C19—H19 | 117.4 |
C6—C5—H5 | 120.5 | C21—C20—C25 | 121.0 (3) |
C5—C6—C1 | 120.2 (3) | C21—C20—S1 | 119.5 (2) |
C5—C6—C7 | 132.2 (3) | C25—C20—S1 | 119.5 (3) |
C1—C6—C7 | 107.5 (2) | C22—C21—C20 | 119.3 (4) |
C8—C7—C12 | 119.6 (2) | C22—C21—H21 | 120.4 |
C8—C7—C6 | 131.9 (2) | C20—C21—H21 | 120.4 |
C12—C7—C6 | 108.5 (2) | C23—C22—C21 | 120.6 (4) |
C7—C8—C9 | 119.2 (2) | C23—C22—H22 | 119.7 |
C7—C8—H8 | 120.4 | C21—C22—H22 | 119.7 |
C9—C8—H8 | 120.4 | C22—C23—C24 | 119.9 (4) |
C8—C9—C10 | 121.1 (2) | C22—C23—H23 | 120.0 |
C8—C9—C19 | 120.2 (2) | C24—C23—H23 | 120.0 |
C10—C9—C19 | 118.8 (2) | C23—C24—C25 | 121.3 (4) |
C11—C10—C9 | 119.4 (2) | C23—C24—H24 | 119.4 |
C11—C10—C13 | 123.7 (2) | C25—C24—H24 | 119.4 |
C9—C10—C13 | 116.9 (2) | C24—C25—C20 | 117.9 (4) |
C12—C11—C10 | 118.3 (2) | C24—C25—H25 | 121.1 |
C12—C11—H11 | 120.9 | C20—C25—H25 | 121.1 |
C10—C11—H11 | 120.9 | C12—N1—C1 | 107.6 (2) |
C11—C12—C7 | 122.4 (2) | C12—N1—S1 | 125.03 (17) |
C11—C12—N1 | 130.0 (2) | C1—N1—S1 | 123.60 (18) |
C7—C12—N1 | 107.5 (2) | C19—N2—C18 | 117.3 (2) |
C14—C13—C18 | 117.8 (2) | O2—S1—O1 | 120.34 (13) |
C14—C13—C10 | 123.8 (2) | O2—S1—N1 | 106.19 (12) |
C18—C13—C10 | 118.5 (2) | O1—S1—N1 | 106.70 (12) |
C15—C14—C13 | 121.3 (3) | O2—S1—C20 | 108.65 (14) |
C15—C14—H14 | 119.3 | O1—S1—C20 | 108.92 (15) |
C13—C14—H14 | 119.3 | N1—S1—C20 | 104.97 (12) |
C14—C15—C16 | 120.2 (3) | ||
C6—C1—C2—C3 | 1.1 (4) | C16—C17—C18—N2 | −179.5 (3) |
N1—C1—C2—C3 | −176.1 (3) | C16—C17—C18—C13 | 0.5 (4) |
C1—C2—C3—C4 | −0.3 (5) | C14—C13—C18—N2 | 179.8 (3) |
C2—C3—C4—C5 | −0.8 (5) | C10—C13—C18—N2 | 0.0 (4) |
C3—C4—C5—C6 | 1.1 (5) | C14—C13—C18—C17 | −0.2 (4) |
C4—C5—C6—C1 | −0.3 (4) | C10—C13—C18—C17 | 180.0 (2) |
C4—C5—C6—C7 | 176.9 (3) | C8—C9—C19—N2 | 179.1 (3) |
C2—C1—C6—C5 | −0.9 (4) | C10—C9—C19—N2 | −0.2 (5) |
N1—C1—C6—C5 | 176.9 (2) | C25—C20—C21—C22 | −1.2 (4) |
C2—C1—C6—C7 | −178.7 (3) | S1—C20—C21—C22 | 179.9 (2) |
N1—C1—C6—C7 | −0.9 (3) | C20—C21—C22—C23 | 2.0 (5) |
C5—C6—C7—C8 | 0.0 (5) | C21—C22—C23—C24 | −1.1 (6) |
C1—C6—C7—C8 | 177.4 (3) | C22—C23—C24—C25 | −0.5 (6) |
C5—C6—C7—C12 | −177.5 (3) | C23—C24—C25—C20 | 1.2 (5) |
C1—C6—C7—C12 | 0.0 (3) | C21—C20—C25—C24 | −0.4 (4) |
C12—C7—C8—C9 | −1.1 (4) | S1—C20—C25—C24 | 178.5 (2) |
C6—C7—C8—C9 | −178.3 (3) | C11—C12—N1—C1 | −178.7 (2) |
C7—C8—C9—C10 | 0.6 (4) | C7—C12—N1—C1 | −1.4 (3) |
C7—C8—C9—C19 | −178.7 (3) | C11—C12—N1—S1 | 22.5 (4) |
C8—C9—C10—C11 | 0.2 (4) | C7—C12—N1—S1 | −160.13 (18) |
C19—C9—C10—C11 | 179.6 (2) | C6—C1—N1—C12 | 1.4 (3) |
C8—C9—C10—C13 | 179.9 (2) | C2—C1—N1—C12 | 179.0 (3) |
C19—C9—C10—C13 | −0.8 (4) | C6—C1—N1—S1 | 160.52 (19) |
C9—C10—C11—C12 | −0.7 (4) | C2—C1—N1—S1 | −21.9 (4) |
C13—C10—C11—C12 | 179.7 (2) | C9—C19—N2—C18 | 1.1 (5) |
C10—C11—C12—C7 | 0.2 (4) | C17—C18—N2—C19 | 179.1 (3) |
C10—C11—C12—N1 | 177.2 (2) | C13—C18—N2—C19 | −0.9 (4) |
C8—C7—C12—C11 | 0.6 (4) | C12—N1—S1—O2 | −163.8 (2) |
C6—C7—C12—C11 | 178.5 (2) | C1—N1—S1—O2 | 40.7 (2) |
C8—C7—C12—N1 | −176.9 (2) | C12—N1—S1—O1 | −34.3 (3) |
C6—C7—C12—N1 | 0.9 (3) | C1—N1—S1—O1 | 170.2 (2) |
C11—C10—C13—C14 | 0.7 (4) | C12—N1—S1—C20 | 81.2 (2) |
C9—C10—C13—C14 | −179.0 (2) | C1—N1—S1—C20 | −74.3 (2) |
C11—C10—C13—C18 | −179.5 (2) | C21—C20—S1—O2 | −19.3 (3) |
C9—C10—C13—C18 | 0.9 (3) | C25—C20—S1—O2 | 161.8 (2) |
C18—C13—C14—C15 | 0.0 (4) | C21—C20—S1—O1 | −152.1 (2) |
C10—C13—C14—C15 | 179.8 (3) | C25—C20—S1—O1 | 29.0 (3) |
C13—C14—C15—C16 | −0.1 (5) | C21—C20—S1—N1 | 94.0 (2) |
C14—C15—C16—C17 | 0.4 (5) | C25—C20—S1—N1 | −84.9 (2) |
C15—C16—C17—C18 | −0.6 (5) |
Cg1 is the centroid of ring C13–C18 and Cg2 is the centroid of ring C7–C12. |
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2···O2 | 0.93 | 2.36 | 2.944 (4) | 121 |
C11—H11···O1 | 0.93 | 2.34 | 2.940 (3) | 122 |
C21—H21···N2i | 0.93 | 2.64 | 3.476 (4) | 150 |
C4—H4···Cg1ii | 0.93 | 2.80 | 3.605 (4) | 145 |
C16—H16···Cg3iii | 0.93 | 2.99 | 3.747 (3) | 139 |
Symmetry codes: (i) x−1/2, −y+1/2, z+1/2; (ii) x−1/2, −y−1/2, z−1/2; (iii) −x+3/2, y+1/2, −z+1/2. |
Acknowledgements
The authors thank the SAIF, IIT, Madras, India, for the data collection.
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